Metakoalin Solid Ionic Conductor and a Sodium-Ion Battery Using the Same

ABSTRACT

A sodium-ion battery comprising a biochar-based anode layer, an NaNiO 2  cathode layer, and an metakaolin solid electrolyte pellets layer.

CROSS REFERENCE TO RELATED APPLICATIONS

This patent application is a continuation of U.S. patent applicationSer. No. 16/378,111, filed on Apr. 8, 2019, which claims the benefit,under 35 U.S.C. § 119(e), of U.S. Provisional Patent Application Ser.No. 62/657,679, filed on Apr. 13, 2018, the content of which isincorporated herein by reference in its entirety.

TECHNICAL FIELD

The present teaching relates generally to sodium-ion batteries. Morespecifically, the present teaching relates to sodium-ion batteriesproduced using a biochar-based anode, NaNiO₂ cathode, and a newmetakaolin solid electrolyte derived from the calcination of kaolinite,proved to be cost-effective and a safe alternative to current batterytechnologies in the realm of energy storage systems.

BACKGROUND

The challenges of fossil fuel-driven climate change and increasingglobal energy demands have given rise to renewable energy power grids.However, the intermittent energy production associated with wind andsolar power generation techniques means that modern grids now requireintermediate energy storage systems (ESSs) consisting of largebatteries. This necessity for grid-scale energy storage has become sogreat that it is projected to be an industry worth at least $250 billionworldwide by 2040.

Lithium-ion batteries (LIBs) have been a technological mainstay for thelast two decades, but many issues are associated with their use in ESSs.ESS applications prioritize safety, cost-effectiveness, and longevity.LIBs do not meet these criteria; though possessing great energy density,LI Bs employ volatile liquid electrolytes (LEs) that can combust in thepresence of air or lead to thermal runaway. In addition, the worldsupply of mineable lithium is rapidly being depleted and is evenprojected to be exhausted within 65 years, making LIBs even moreexpensive.

Sodium is 2000 times as abundant and 37 times as cheap as lithium andcan be used in sodium-ion batteries (SIBs) analogous to LIBs. SIBs,however, are made with similar LEs and are thus plagued with the samesafety issues as LIBs. They also suffer from performance deficiencies insuch areas as capacity and overall energy density, which limits theirability to replace LIBs in areas like ESSs.

Through intrinsically safe and cost-effective aqueous electrolytes are aviable alternative to aprotic organic electrolytes in SIBs, batteriesemploying them tend to suffer in performance and are not long-lastingdue to electrode degradation. Therefore, a superior alternative would bethe implementation of solid electrolytes (SEs) in SIBs. SEs arecharacterized with greater thermal stability than LEs and also eliminatethe risk of electrolyte leaks—a danger that could prove catastrophic ingrid-scale batteries. In addition, SEs facilitate the incorporation ofsodium metal anodes into SIB systems. Metallic Na anodes possessunparalleled capacity but are prone to dendritic growth that canshort-circuit liquid electrolyte batteries.

However, the most prominent SEs in literature—B-alumina and sodiumsuperionic conductor (NASICON)—are greatly limited in their performanceand industrial scalability. For instance, B-alumina needs to be heatedto high temperatures to conduct sodium ions, which complicates operationat room temperature and in some battery systems can lead to explosion.In general, very few SEs have high Na+ conductivity at room temperature,with the exception of NASICON. NASICON, however, requires multiple hightemperature firings to refine its crystal grain for effective chargeconduction, as well as sintering to the electrodes with which it isused. The problematic surface grain of NASICON also renders itincompatible with most conventional cathode materials. Consequently,current SIB architectures utilizing NASICON are difficult tomass-produce and are not cost-effective.

Therefore, it would be beneficial to have a cost-effective sodium-ionbattery that can be mass produced and which can be incorporated into theESSs of smart power grids relying on renewable energy and a solidelectrolyte.

SUMMARY

The needs set forth herein as well as further and other needs andadvantages are addressed by the present embodiments, which illustratesolutions and advantages described below.

The sodium-ion battery of one embodiment, according to the presentteaching, includes, but is not limited to, a biochar-based anode layer,an NaNiO₂ cathode layer, and a metakaolin solid electrolyte pelletslayer.

In a further embodiment, the biochar-based anode comprises biocharpelletized with a steel die.

In a further embodiment, the NaNiO₂ cathode comprises a mixture ofpolyvinylidene difluoride, carbon black, and sodium nickel dioxidecombined with deionized water to form a slurry.

In a further embodiment, the NaNiO₂ cathode is formed by laying theslurry onto an aluminum plate.

In a further embodiment, the metakaolin solid electrolyte pellets arederived from a calcination of kaolinite.

In a further embodiment, the biochar-based anode, NaNiO₂ cathode, andthe metakaolin solid electrolyte pellets are layered on an aluminumcurrent collector. The biochar-based anode is layered first, then themetakaolin solid electrolyte pellets are layered, then the NaNiO₂cathode is layered.

In a further embodiment, the aluminum current collector is placed on aspacer plate and into a positive bottom of a coin cell, a second spacerplate is placed on the NaNiO2 cathode, a spring is placed on the secondspacer plate, and a negative lid of the coin cell is placed on top ofthe spring to close the coin cell.

In a further embodiment, the sodium-ion battery is used in a power gridas an energy storage source. According to further embodiments, thesodium-ion battery can also be used in, but is not limited to,electronics, vehicles, and other battery-operated equipment, as anenergy storage source.

In a further embodiment, a power grid includes an energy storage sourcehaving a plurality of the sodium-ion battery.

One method for assembling a sodium-ion battery of another embodiment,according to the present teaching, includes, but is not limited tolayering a biochar-based anode, an NaNiO₂ cathode, and a metakaolinelectrolyte pellet on an aluminum current collector.

In a further embodiment, the biochar-based anode is formed bypelletizing biochar with a steel die to form biochar pellets.

In a further embodiment, the NaNiO₂ cathode is formed by combiningpolyvinylidene difluoride, carbon black, and sodium nickel dioxide mixedwith deionized water to form a slurry and layering the slurry onto analuminum plate and drying the slurry.

In a further embodiment, the metakaolin electrolyte pellets are formedby compressing kaolinite powder into pellets and heating the pellets.

In a further embodiment, the biochar-based anode is layered first, thenthe metakaolin solid electrolyte pellets are layered, then the NaNiO₂cathode is layered.

In a further embodiment, the aluminum current collector is placed on aspacer plate and into a positive bottom of a coin cell, a second spacerplate is placed on the NaNiO2 cathode, a spring is placed on the secondspacer plate, and a negative lid of the coin cell is placed on top ofthe spring to close the coin cell.

In a further embodiment, the sodium-ion battery is used in a power gridas an energy storage source. According to further embodiments, thesodium-ion battery can also be used in, but is not limited to,electronics, vehicles, and other battery-operated equipment, as anenergy storage source.

In a further embodiment, a power grid includes an energy storage sourcehaving a plurality of the sodium-ion battery.

Another method for assembling a sodium-ion battery of anotherembodiment, according to the present teaching, includes, but is notlimited to layering a biochar-based anode, an NaNiO₂ cathode, and ametakaolin electrolyte pellet on an aluminum current collector. Thebiochar-based anode is formed by pelletizing biochar with a steel die toform biochar pellets. The NaNiO₂ cathode is formed by combiningpolyvinylidene difluoride, carbon black, and sodium nickel dioxide mixedwith deionized water to form a slurry and laying the slurry onto analuminum plate and drying said slurry. The metakaolin electrolytepellets are formed by compressing kaolinite powder into pellets andheating said pellets. The biochar-based anode is layered first, then themetakaolin solid electrolyte pellets are layered, then the NaNiO₂cathode is layered. The aluminum current collector is placed on a spacerplate and into a positive bottom of a coin cell, a second spacer plateis placed on the NaNiO2 cathode, a spring is placed on the second spacerplate, and a negative lid of the coin cell is placed on top of thespring to close the coin cell.

Other embodiments of the system and method are described in detail belowand are part of the present teachings.

For a better understanding of the present embodiments, together withother and further aspects thereof, reference is made accompanyingdrawings and detailed description, and its scope will be pointed out inthe appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an exploded perspective view of an electrochemical cell.

FIG. 2 is an attenuated total reflection-Fourier-transform infraredspectroscopy (ATR-FTIR) spectra for kaolinite (Al₂Si₂O₅(OH)₄).

FIG. 3 is an ATR-FTIR spectra for metakaolin (Al₂Si₂O₇).

FIG. 4 is an ATR-FTIR spectra of synthesized NaNiO₂ powder, Na₂CO₃grains, and Ni(NO₃)₂ crystals, with Ni—O vibrations indicated at 847cm⁻¹.

FIG. 5 is a discharge potential of MSE SIB after being charged at 2V for3 h.

FIG. 6 is a discharge current (A) and power (B) of MSE SIB after beingcharged at 2V for 3 h.

FIG. 7 is a potential and capacity discharge profile of MSE SIB afterbeing charged for 3 h at 2V.

FIG. 8 is a logarithmic trendline function of MSE SIB dischargepotential after being charged at 2V for 3 h (A) and translated trendlineto simulate theoretical capacity with 20 mm-diameter cell components(B).

FIG. 9 is a mathematical model linking MSE SIB cell potential withtheoretical current output via experimental MSE ionic conductivity data.

FIG. 10 is a discharge potential of LE SIB.

FIG. 11 is a discharge potential of LE SIB with an improved cathode.

FIG. 12 is a MSE SIB capacity (A) and voltage efficiency (B) over 20cycles with 2V, 2 h charge regimen and discharge duration of 1 h.

FIG. 13 is a MSE SIB capacity (A) and voltage efficiency (B) over 20cycles with 2V, 2 h charge regimen and discharge potential limit of0.1V.

FIG. 14 is a XRD spectrum of a pulverized MSE pellet, in which there arevisible distinct crystalline silica phases between ˜20° 2θ and 27° 2θ aswell as amorphous alumina phases between 10° 2θ and 2θ° 2θ.

DETAILED DESCRIPTION

The present teachings are described more fully hereinafter withreference to the accompanying drawings, in which the present embodimentsare shown. The following description is presented for illustrativepurposes only and the present teachings should not be limited to theseembodiments.

In compliance with the statute, the present teachings have beendescribed in language more or less specific as to structural andmethodical features. It is to be understood, however, that the presentteachings are not limited to the specific features shown and described,since the systems and methods herein disclosed comprise preferred formsof putting the present teachings into effect.

For purposes of explanation and not limitation, specific details are setforth such as particular architectures, interfaces, techniques, etc. inorder to provide a thorough understanding. In other instances, detaileddescriptions of well-known devices, circuits, and methods are omitted soas not to obscure the description with unnecessary detail.

Generally, all terms used in the claims are to be interpreted accordingto their ordinary meaning in the technical field, unless explicitlydefined otherwise herein. All references to a/an/the element,composition, apparatus, component, means, step, etc., are to beinterpreted openly as referring to at least one instance of the element,composition, apparatus, component, means, step, etc., unless explicitlystated otherwise. The steps of any method disclosed herein do not haveto be performed in the exact order disclosed, unless explicitly stated.The use of “first,” “second,” etc. for different features/components ofthe present disclosure are only intended to distinguish thefeatures/components from other similar features/components and not toimpart any order or hierarchy to the features/components.

To aid the Patent Office and any readers of any patent issued on thisapplication in interpreting the claims appended hereto, Applicant doesnot intend any of the appended claims or claim elements to invoke 35U.S.C. 112(f) unless the words “means for” or “step for” are explicitlyused in the particular claim.

The sodium-ion battery, according to one embodiment, includes an anode,a cathode, and an electrolyte. The cathode was prepared with apolyvinylidene difluoride (PVdF), carbon black, and NaNiO₂ powdermixture using the process described in De Silva et al., “Sodium nickeloxide nanoporous cathodes used for sodium-ion rechargeable batteries,”vol. 15, pp. 19-29, 2014. A slurry was obtained by adding the powdermixture to di-H₂O. The slurry was then layered onto a circular aluminum(Al) plate 15 mm in diameter and allowed to dry to produce a standardNIB NaNiO₂ cathode. The anode was prepared by substituting biochar forthe hard carbon in the procedure found in Kim et al., “Na ion-ConductingCeramic as Solid Electrolyte for Recharging Seawater Batteries,”Electrochim. Acta, vol. 191, pp. 1-7, 2016. The resultant mixture wasthen pelletized with a steel die as done in the manufacturing of solidelectrolyte (SE) pellets. The electrolyte was prepared first with theproduction of metakaolin SE (MSE) pellets. The pellets were producedwith a one step calcination process. This resulted in thedehydroxylization of the kaolinite and the formation of a dense ceramic:

Al₂Si₂O₅(OH)₄→Al₂Si₂O₇+2H₂O

The kaolinite powder was placed into a 13 mm steel evacuable die andcompressed into a vice to form a 1 mm thick pellet. The pellet was thenheated in a furnace at ˜1000° C. for ˜4 hours.

Referring now to FIG. 1, the figure shows, by way of a non-limitingexample, an exploded perspective view of the electrochemical CR2032 fullcoin cell. A case lid (26) and a case bottom (18) contain the cell andserve as the positive and negative terminals respectively. Placed insidethe negative case bottom (18) is a spacer plate (20), followed by thebiochar-based anode covered aluminum current collector (12), themetakaolin solid electrolyte pellets (14), and the NaNiO₂ cathode (16).To complete the cell (10) a second spacer plate (22) is placed on top ofthe cathode (16), followed by a spring (24) and topped off with thepositive case lid (26).

According to one embodiment the coin cell case lid (26) can be at leasta stainless steel lid.

According to one embodiment the coin cell case bottom (18) can be atleast a special oxidation resistant case bottom.

According to one embodiment the coin cell case lid (26) can be negativeand the coin cell case bottom (18) can be positive.

CR2032 full cell batteries were assembled and sealed in an N₂ atmosphereby layering the synthesized carbonaceous anodes, MSE pellets, and NaNiO₂cathodes atop 16 mm-diameter circular Al current collectors withinCR2032 coin cell casings, as shown in FIG. 1.

According to one embodiment, the CR2032 batteries can also be assembledand sealed in any other inert atmosphere, including argon.

Referring now to FIG. 2, the figure shows an attenuated totalreflectance Fourier transform infrared (ATR-FTIR) spectra for kaolinite.

Referring now to FIG. 3, the figure shows an attenuated totalreflectance Fourier transform infrared (ATR-FTIR) spectra formetakaolin.

The comparisons of FIG. 2 and FIG. 3 show the disappearance of Al—OHvibrations as well as Al—O—Si vibrations from the kaolinite due tocalcination.

Referring now to FIG. 4, the figure shows the attenuated totalreflectance Fourier transform infrared (ATR-FTIR) spectra forsynthesized NaNiO₂ powder as well as its Na₂CO₃ and Ni(NO₃)₂ precursors.The ATR-FTIR was used to validate the synthesis of the NaNiO₂ cathodematerial, as the Ni—O vibrations in the NaNiO₂ sample around 847 cm⁻¹were consistent with those reported in De Silva et al., “Sodium nickeloxide nanoporous cathodes used for sodium-ion rechargeable batteries,”vol. 15, pp. 19-29, 2014.

Referring now to FIG. 5, the figure shows the experimental results whenthe test cells were subsequently cycled utilizing a simple circuit thatwas constructed with an Arduino Mega microcontroller and a 25V, 5 AEntek DC transformer. The results indicated that MSE SIBs could operateat 1.1V at room temperature after being charged at 2V for 3 hours. Thissuggests a voltage efficiency of ˜55%, though cell potential was almostentirely dependent on the electrode materials employed and theircompatibility with the MSE.

A typical cycling regimen for an MSE SIB involved potentiostaticcharging at 2-5V for 0.5-6 hour durations, after which the cells woulddischarge wither for a set amount of time (1-2 hours) or until theyattained a minimum potential (0.1 V). MSE SIBs were put through 20-100cycles at a time and ˜200 cycles total.

Referring now to FIG. 6, the figure shows the discharge current (A) andpower (b) of MSE SIB after being charged at 2V for 3 hours. This showsthat the current fade during discharge and its subsequent effect on cellpower can also be attributed to the capacity of the biochar anodes.

Referring now to FIG. 7, the figure shows the potential and capacitydischarge profiles of MSE SIB after being charged for 3 hours at 2V.Maximum capacity was found to be 5.5 mAh after a 2V, 3 hour chargeregimen. However, because only 13 mm-diameter MSE pellets and anodeswere produced due to equipment limitations, only 42% of the internalavailable surface area within the 20 mm CR2032 cell casings was beingemployed.

Referring now to FIG. 8, the figure shows a logarithmic trendlinefunction of MSE SIB discharge potential after being charged at 2V for 3hours (A) and a translated trendline to simulate theoretical capacitywith 20 mm-diameter cell. These trendlines showed that the cells weretheoretically capable of ˜8.7 mAh with considerably less dischargecurrent, voltage, and power fade.

Referring now to FIG. 9, the figure shows a mathematical model linkingMSE SIB cell potential with theoretical current output via experimentalMSE ionic conductivity. The relationship between cell potential andcurrent output was studied more closely within the context of the ionicconductivity of the MSE pellets. Ionic conductivity during celldischarge was found utilizing the following equation: C=1N*d/A where Cis ionic conductivity in S/cm, I is current output in amps, V is voltageoutput, d is the distance between the electrodes—or the MSE pelletthickness in cm (0.15875 cm in this research), and A is the effectivearea of the cell electrodes in cm² (132.732 in this research). Betweenall discharge measurements of all cycles of all of the MSE SIBs, theeffective ionic conductivity was always found to be 5.73×10⁻⁸ S/cm. Fromthis data was extrapolated the simple mathematical model:I(V)=4.79097×10⁻⁷V in which I (current measured in amps) is representedas a function of V (cell potential). This model indicates that if MSESIBs were constructed using more high performance electrodes capable of,for instance, a 3.8V cell potential as reported in literature, the MSEwould facilitate a maximum current output of 0.0018 mA—three times asmuch as the 0.0006 mA shown in this research.

It is important to note, though, that 5.73×10⁻⁸ S/cm was the effectiveionic conductivity found. The value signifies the maximum conductivityachieved by the MSE when in combination with the electrode materialsthat were implemented, suggesting that the conductivity can be greaterwith higher-performance electrode materials. Representative of thisassertion was the relatively poor performance exhibited by the controlLE SIBs and the aggrandized performance that was later achieved withmodification of the electrodes.

Referring now to FIG. 10, the figure shows the discharge potential of LESIB. The LE SIBs produced a maximum voltage of 0.33 volts while usingthe same electrode materials as the MSE SIBs, demonstrating theshortcomings of the use of the simple and cost-effective standardelectrodes with LEs.

Referring now to FIG. 11, the figure shows the discharge potential of LESIB with an improved cathode. An experimental LE SIB cell wasconstructed with an NaNiO₂ cathode created fromN-methyl-2-pyrrolidone-based slurry rather than a di-H₂O one. Theimproved binder helped mitigate dissolution of the electrode into theLE, resulting in improved performance.

Even with improvements, none of the LE SIB cells were functional beyondtwo cycles, implying that the LE was not able to form efficient andreversible electrochemical complexes with the electrode materials. Incontrast, MSE SIBs saw no loss of capacity even beyond 200 total cycles;furthermore, they showed great durability when it came to over-chargingand over-discharging.

Referring now to FIG. 12, the figure shows the MSE SIB capacity (A) andvoltage efficiency (B) where when cycled 20 times on a 2V, 2 h chargeregimen with discharge duration limited to 1 h, MSE SIB output wascharacterized with relatively stable reversible capacity and voltageefficiency.

Referring now to FIG. 13, the figure shows the MSE SIB capacity (A) andvoltage efficiency (B) where the MSE SIBs cycled 20 times on a 2V andallowed to discharge to a minimum voltage of 0.1 V so that capacitywould be reduced with each consecutive cycle. In this test, capacityremained fully reversible during and after the test and voltageefficiency, though also diminished in the test, was stable.

To develop a hypothesis regarding how this conduction mechanism mightfunction, metakaolin's unique structure was investigated morethoroughly. X-ray diffraction (XRD) was utilized to explore thecharacteristics of the silica and alumina groups that make up thestructure. The analysis was conducted with powder derived frompulverizing an SE pellet in an agate mortar.

Referring now to FIG. 14, the figure shows the resultant spectrumindicated an array of unique and distinct silica crystal phases between˜20° 2θ and 27° 2θ as well as an amorphous nature to alumina structuresbetween 10° 2θ and 20° 2θ. Alumina groups in the kaolinite were alteredsignificantly when dehydroxylized during the calcination process; thissubsequently led to the reformation of silica crystal phases to adapt tothe structural changes, for a net result of a complex metakaolinstructure characterized with a high degree of disorder.

While the present teachings have been described above in terms ofspecific embodiments, it is to be understood that they are not limitedto these disclosed embodiments. Many modifications and other embodimentswill come to mind to those skilled in the art to which this pertains,and which are intended to be and are covered by both this disclosure andthe appended claims. It is intended that the scope of the presentteachings should be determined by proper interpretation and constructionof the appended claims and their legal equivalents, as understood bythose of skill in the art relying upon the disclosure in thisspecification and the attached drawings.

What is claimed:
 1. A method for assembling a sodium-ion batterycomprising: layering a biochar-based anode, an NaNiO₂ cathode, and ametakaolin electrolyte pellet on an aluminum current collector.
 2. Themethod of claim 1, wherein said biochar-based anode is formed bypelletizing biochar with a steel die to form biochar pellets.
 3. Themethod of claim 1, wherein said NaNiO2 cathode is formed by combiningpolyvinylidene difluoride, carbon black, and sodium nickel dioxide mixedwith deionized water to form a slurry; and laying said slurry onto analuminum plate and drying said slurry.
 4. The method of claim 1, whereinsaid metakaolin electrolyte pellets are formed by compressing kaolinitepowder into pellets and heating said pellets.
 5. The method of claim 1,wherein said biochar-based anode is layered first on said aluminumcurrent collector, then said metakaolin solid electrolyte pellets arelayered, then said NaNiO2 cathode is layered.
 6. The method of claim 5,wherein said aluminum current collector is placed on a first spacerplate and into a positive bottom of a coin cell, a second spacer plateis placed on said NaNiO2 cathode, a spring is placed on said secondspacer plate, and a negative lid of said coin cell is placed on top ofsaid spring to close said coin cell.
 7. The method of claim 1, wherein aplurality of said sodium-ion battery are used in a power grid as anenergy storage source.
 8. A method for assembling a sodium-ion batterycomprising: layering a biochar-based anode, an NaNiO₂ cathode, and ametakaolin electrolyte pellet on an aluminum current collector; whereinsaid biochar-based anode is formed by pelletizing biochar with a steeldie to form biochar pellets; wherein said NaNiO₂ cathode is formed bycombining polyvinylidene difluoride, carbon black, and sodium nickeldioxide mixed with deionized water to form a slurry and laying saidslurry onto an aluminum plate and drying said slurry; wherein saidmetakaolin electrolyte pellets are formed by compressing kaolinitepowder into pellets and heating said pellets; wherein said biochar-basedanode is layered first on said aluminum current collector, then saidmetakaolin solid electrolyte pellets are layered, then said NaNiO₂cathode is layered; and wherein said aluminum current collector isplaced on a first spacer plate and into a positive bottom of a coincell, a second spacer plate is placed on said NaNiO2 cathode, a springis placed on said second spacer plate, and a negative lid of said coincell is placed on top of said spring to close said coin cell.
 9. Amethod for assembling a sodium-ion battery comprising: layering abiochar-based anode, a NaNiO₂ cathode, and a metakaolin electrolyte. 10.The method of claim 9, wherein the anode, cathode, and metakaolinelectrolyte are layered on a current collector.
 11. The method of claim10, wherein said biochar-based anode is layered first on said currentcollector, then said metakaolin solid electrolyte is layered, then saidNaNiO2 cathode is layered.
 12. The method of claim 11, wherein saidcurrent collector is placed on a first spacer plate and into a positivebottom of a coin cell, a second spacer plate is placed on said NaNiO2cathode, a spring is placed on said second spacer plate, and a negativelid of said coin cell is placed on top of said spring to close said coincell.
 13. The method of claim 9, wherein said biochar-based anode isprovided as pellets.
 14. The method of claim 9, wherein said NaNiO2cathode is formed by combining polyvinylidene difluoride, carbon black,and sodium nickel dioxide.
 15. The method of claim 9, wherein saidmetakaolin electrolyte are provided as pellets.
 16. The method of claim9, wherein a plurality of said sodium-ion battery are used in a powergrid as an energy storage source.
 17. A sodium ion battery madeaccording to the method of claim
 9. 18. A plurality of sodium ionbatteries made according to the method of claim 9, used in a power gridas an energy storage source.